Preparation and DFT studies of chiral Cu (I)-complexes of biphenyl bisoxazolines and their application in enantioselective Kharasch–Sosnovsky reaction

• Published in: Scientific reports Vol. 12; no. 1; p. 15038
• Main Authors: Samadi, Saadi, Arvinnezhad, Hamid, Mansoori, Sirwan, Parsa, Hadi
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 03.09.2022; Nature Publishing Group; Nature Portfolio
• Subjects: 639/638/403; 639/638/403/935; 639/638/549/972; 639/638/77/883; 639/638/77/888; Biphenyl; Chelation; Chemical activity; Copper; Enantiomers; Equilibrium; Esters; Humanities and Social Sciences; Ligands; multidisciplinary; Oxidation; Porous materials; Science; Science (multidisciplinary); Temperature
• ISSN: 2045-2322; 2045-2322
• DOI: 10.1038/s41598-022-18922-1

Effect of a range of t -butyl perbenzoates bearing electron-withdrawing and electron-donating substitutions on the phenyl ring and HZSM-5 as a porous additive at 0 °C in enantioselective allylic C–H bond oxidation of cyclic and acyclic olefins in the presence of Cu (I)-( S, a S,S ) complexes of biphenyl bisoxazoline ligands, produced easily through the chelation-induced process, were investigated. The enantioenriched allylic esters were obtained in reasonable times with excellent enantioselectivities and yields using electron-withdrawing substituted peresters in the presence of Cu (I)-( S, a S,S ) -1a complex, containing phenyl groups at the stereogenic centers of the oxazoline moieties. To reach a better insight on geometry, chemical activity, enantioselectivity, and thermodynamic stability of the Cu (I)-BOX complexes, DFT calculations with B3LYP-D3/6-31G ( d , p ) level of theory were applied to them. Moreover, NBO analysis was used to illustrate interactions between orbitals.